不同浓度Sn<sup>4+</sup>离子掺杂TiO<sub>2</sub>的结构、性质和光催化活性

引用本文: 张鹏, 赵路松, 姚江宏, 曹亚安. 不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性[J]. 物理化学学报, 2013, 29(06): 1305-1312. doi: 10.3866/PKU.WHXB201303182 shu

Citation: ZHANG Peng, ZHAO Lu Song, YAO Jiang Hong, CAO Ya An. Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions[J]. Acta Physico-Chimica Sinica, 2013, 29(06): 1305-1312. doi: 10.3866/PKU.WHXB201303182 shu

不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性

基金项目:
国家自然科学基金(51072082, 21173121, 11074129) (51072082, 21173121, 11074129)

国家重点基础研究发展规划项目(973) (2012CB934201)资助 (973) (2012CB934201)

摘要:

采用溶胶-凝胶法制备出纯TiO₂和不同浓度Sn⁴⁺离子掺杂的TiO₂光催化剂(TiO₂-Snx%, x%代表Sn⁴⁺离子掺杂的TiO₂样品中Sn⁴⁺离子摩尔分数). 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)和表面光电压谱(SPS)确定了TiO₂-Snx%催化剂的晶相结构和能带结构, 结果表明: 当Sn⁴⁺离子浓度较低时, Sn⁴⁺离子进入TiO₂晶格, 取代并占据Ti⁴⁺离子的位置, 形成取代式掺杂结构(Ti_1-xSn_xO₂), 其掺杂能级在导带下0.38 eV处; 当Sn⁴⁺离子浓度较高时, 掺入的Sn⁴⁺离子在TiO₂表面生成金红石SnO₂, 形成TiO₂和SnO₂复合结构(TiO₂/SnO₂), SnO₂的导带位于TiO₂导带下0.33 eV处. 利用瞬态光电压谱和荧光光谱研究了TiO₂-Snx%催化剂光生载流子的分离和复合的动力学过程, 结果表明, Sn⁴⁺离子掺杂能级和表面SnO₂能带存在促进光生载流子的分离, 有效地抑制了光生电子与空穴的复合; 然而, Sn⁴⁺离子掺杂能级能更有效地增加光生电子的分离寿命, 提高了光生载流子的分离效率, 从而揭示了TiO₂-Snx%催化剂的光催化机理.

关键词:

English

Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions

1.
1 College of Physics, Nankai University, Tianjin 300071, P. R. China;
2 Key Laboratory of Weak Light Nonlinear Photonics, Ministry of Education, Teda Applied Physics School, Nankai University, Tianjin 300457, P. R. China
Received Date: 11 December 2012
Available Online: 17 May 2013
Fund Project:
国家自然科学基金(51072082, 21173121, 11074129)

国家重点基础研究发展规划项目(973) (2012CB934201)资助

Abstract:

Pure TiO₂ and Sn⁴⁺ doped TiO₂ (TiO₂-Snx%) photocatalysts were prepared by a sol-gel method, where x% represents the nominal molar fraction of Sn⁴⁺ ions in the Zr⁴⁺ structure. The crystal structure and energy band structure of the resultant catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and surface photovoltage spectroscopy (SPS).The results show that for a low content of Sn⁴⁺ ions, the Sn⁴⁺ ions are doped into the TiO₂ lattice and replace lattice Ti⁴⁺ ions in a substitute mode (Ti_1-xSn_xO₂). The energy levels of these Sn⁴⁺ ions are located 0.38 eV below the conduction band. Moreover, the rutile SnO₂ crystal structure evolves with increasing content of Sn⁴⁺ ions, i.e., a TiO₂/SnO₂ structure is formed. The conduction band of SnO₂ is located 0.33 eV lower than that of TiO₂. The separation and recombination mechanism of the photo-generated carriers was characterized by photoluminescence and transient photovoltage techniques. The results showed that the formation of the energy levels of Sn⁴⁺ ions and the conduction band of rutile SnO₂ can enhance the separation of the photogenerated carriers, and suppress the recombination of photo-generated carriers. However, the energy levels of Sn⁴⁺ can lead to a much longer life time and higher separation efficiency of the photo-generated carriers. For different content of Sn⁴⁺ in Sn⁴⁺ ion doped TiO₂(TiO₂-Snx%), the abovementioned aspects improve the photocatalytic activity.

Key words:

Sn⁴⁺-doped TiO₂
/ Content of Sn⁴⁺ ions
/ Transient photovoltage
/ Surface photovoltage spectroscopy
/ Life time of photo-generated electrons

1. [1]
  
  (1) Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
  (1) Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
2. [2]
  (2) Grätzel, M. Nature 2001, 414, 338. doi: 10.1038/35104607(2) Grätzel, M. Nature 2001, 414, 338. doi: 10.1038/35104607
3. [3]
  (3) Khan, S.; Al-Shahry, M.; Ingler,W. Science 2002, 297, 2243.doi: 10.1126/science.1075035(3) Khan, S.; Al-Shahry, M.; Ingler,W. Science 2002, 297, 2243.doi: 10.1126/science.1075035
4. [4]
  (4) Yu, H.; Chen, S.; Quan, X.; Zhao, H.; Zhang, Y. Environ. Sci. Technol. 2008, 42, 3791. doi: 10.1021/es702948e(4) Yu, H.; Chen, S.; Quan, X.; Zhao, H.; Zhang, Y. Environ. Sci. Technol. 2008, 42, 3791. doi: 10.1021/es702948e
5. [5]
  (5) Asahi, R.; Morikawa, T.; Ohwaki, K.; Aoki, K.; Taga, Y. Science2001, 293, 269. doi: 10.1126/science.1061051(5) Asahi, R.; Morikawa, T.; Ohwaki, K.; Aoki, K.; Taga, Y. Science2001, 293, 269. doi: 10.1126/science.1061051
6. [6]
  (6) Francioso, L.; Presicce, D.; Siciliano, P.; Ficarella, A. Sensors and Actuators B 2007, 123, 516. doi: 10.1016/j.snb.2006.09.037(6) Francioso, L.; Presicce, D.; Siciliano, P.; Ficarella, A. Sensors and Actuators B 2007, 123, 516. doi: 10.1016/j.snb.2006.09.037
7. [7]
  (7) Zhao,W.; Ma,W.; Chen, C.; Zhao, J.; Shuai, Z. J. Am. Chem. Soc. 2004, 126, 4782. doi: 10.1021/ja0396753(7) Zhao,W.; Ma,W.; Chen, C.; Zhao, J.; Shuai, Z. J. Am. Chem. Soc. 2004, 126, 4782. doi: 10.1021/ja0396753
8. [8]
  (8) Zhang, J.;Wu, Y.; Xing, M.; Leghari, S.; Sajjad, S. Energy Environ. Sci. 2010, 3, 715. doi: 10.1039/b927575d(8) Zhang, J.;Wu, Y.; Xing, M.; Leghari, S.; Sajjad, S. Energy Environ. Sci. 2010, 3, 715. doi: 10.1039/b927575d
9. [9]
  (9) Ji, P.; Takeuchi, M.; Cuong, T.; Zhang, J.; Matsuoka, M.; Anpo,M. Research on Chemical Intermediates 2010, 36, 327.doi: 10.1007/s11164-010-0142-5(9) Ji, P.; Takeuchi, M.; Cuong, T.; Zhang, J.; Matsuoka, M.; Anpo,M. Research on Chemical Intermediates 2010, 36, 327.doi: 10.1007/s11164-010-0142-5
10. [10]
  (10) Luo, D. C.; Zhang, L. L.; Long, H. J.; Chen, Y. M.; Cao, Y. A.Acta Phys. -Chim. Sin. 2008, 24, 1095. [罗大超, 张兰兰, 龙绘锦, 陈咏梅, 曹亚安. 物理化学学报, 2008, 24, 1095.]doi: 10.3866/PKU.WHXB20080632(10) Luo, D. C.; Zhang, L. L.; Long, H. J.; Chen, Y. M.; Cao, Y. A.Acta Phys. -Chim. Sin. 2008, 24, 1095. [罗大超, 张兰兰, 龙绘锦, 陈咏梅, 曹亚安. 物理化学学报, 2008, 24, 1095.]doi: 10.3866/PKU.WHXB20080632
11. [11]
  (11) Li, K. Y.; Guo, J.; Liu, T.; Zhou, B. J.; Li, Y. Acta Phys. -Chim. Sin. 2008, 24, 2096. [李葵英, 郭静, 刘通, 周冰晶,李悦. 物理化学学报, 2008, 24, 2096.] doi: 10.3866/PKU.WHXB20081127(11) Li, K. Y.; Guo, J.; Liu, T.; Zhou, B. J.; Li, Y. Acta Phys. -Chim. Sin. 2008, 24, 2096. [李葵英, 郭静, 刘通, 周冰晶,李悦. 物理化学学报, 2008, 24, 2096.] doi: 10.3866/PKU.WHXB20081127
12. [12]
  (12) Zhou, X.; Lu, J.; Li, L.;Wang, Z. Journal of Nanomaterials2011, 2011, 432947.(12) Zhou, X.; Lu, J.; Li, L.;Wang, Z. Journal of Nanomaterials2011, 2011, 432947.
13. [13]
  (13) Mahanty, S.; Roy, S.; Sen, S. Journal of Crystal Growth 2004,261, 77. doi: 10.1016/j.jcrysgro.2003.09.023(13) Mahanty, S.; Roy, S.; Sen, S. Journal of Crystal Growth 2004,261, 77. doi: 10.1016/j.jcrysgro.2003.09.023
14. [14]
  (14) Gu, Q.; Long, J.; Zhou, Y.; Yuan, R.; Lin, H.;Wang, X. Journal of Catalysis 2012, 289, 88. doi: 10.1016/j.jcat.2012.01.018(14) Gu, Q.; Long, J.; Zhou, Y.; Yuan, R.; Lin, H.;Wang, X. Journal of Catalysis 2012, 289, 88. doi: 10.1016/j.jcat.2012.01.018
15. [15]
  (15) Zheng, T.; Tian, Z.; Sun, J. X.; Su, B. T.; Lei, Z. Q. Chemical Research and Application 2012, 24, 1. [郑焘, 田泽, 孙佳星, 苏碧桃, 雷自强. 化学研究与应用, 2012, 24, 1.](15) Zheng, T.; Tian, Z.; Sun, J. X.; Su, B. T.; Lei, Z. Q. Chemical Research and Application 2012, 24, 1. [郑焘, 田泽, 孙佳星, 苏碧桃, 雷自强. 化学研究与应用, 2012, 24, 1.]
16. [16]
  (16) Duan, Y.; Fu, N.; Liu, Q.; Fang, Y.; Zhou, X.; Zhang, J.; Lin, Y.J. Phys. Chem. C 2012, 116, 8888. doi: 10.1021/jp212517k(16) Duan, Y.; Fu, N.; Liu, Q.; Fang, Y.; Zhou, X.; Zhang, J.; Lin, Y.J. Phys. Chem. C 2012, 116, 8888. doi: 10.1021/jp212517k
17. [17]
  (17) Cao, Y.; He, T.; Zhao, L.;Wang, E.; Yang,W.; Cao, Y. J. Phys. Chem. C 2009, 113, 18121. doi: 10.1021/jp9069288(17) Cao, Y.; He, T.; Zhao, L.;Wang, E.; Yang,W.; Cao, Y. J. Phys. Chem. C 2009, 113, 18121. doi: 10.1021/jp9069288
18. [18]
  (18) Cao, Y.; Yang, Y.; Zhang,W.; Liu, G.; Yue, P. New J. Chem.2004, 28, 218. doi: 10.1039/b306845e(18) Cao, Y.; Yang, Y.; Zhang,W.; Liu, G.; Yue, P. New J. Chem.2004, 28, 218. doi: 10.1039/b306845e
19. [19]
  (19) Wang, Y.; Ma, C.; Sun, X.; Li, H. Nanotechnology 2002, 13,565. doi: 10.1088/0957-4484/13/5/304(19) Wang, Y.; Ma, C.; Sun, X.; Li, H. Nanotechnology 2002, 13,565. doi: 10.1088/0957-4484/13/5/304
20. [20]
  (20) Li, J.; Zeng, H. J. Am. Chem. Soc. 2007, 129, 15839.doi: 10.1021/ja073521w(20) Li, J.; Zeng, H. J. Am. Chem. Soc. 2007, 129, 15839.doi: 10.1021/ja073521w
21. [21]
  (21) Xu, H.; Zhang, L. J. Phys. Chem. C 2010, 114, 11534.doi: 10.1021/jp1027965(21) Xu, H.; Zhang, L. J. Phys. Chem. C 2010, 114, 11534.doi: 10.1021/jp1027965
22. [22]
  (22) Bullock, E.; Patthey, L.; Steinemann, S. Surface Science 1996,352, 504. doi: 10.1016/0039-6028(95)01188-9(22) Bullock, E.; Patthey, L.; Steinemann, S. Surface Science 1996,352, 504. doi: 10.1016/0039-6028(95)01188-9
23. [23]
  (23) Li, D.; Haneda, H.; Hishita, D.; Ohashi, N. Chem. Mater. 2005,17, 2596. doi: 10.1021/cm049099p(23) Li, D.; Haneda, H.; Hishita, D.; Ohashi, N. Chem. Mater. 2005,17, 2596. doi: 10.1021/cm049099p
24. [24]
  (24) Serpone, N.; Lawless, D.; Khairutdinov, R. J. Phys. Chem.1995, 99, 16646. doi: 10.1021/j100045a026(24) Serpone, N.; Lawless, D.; Khairutdinov, R. J. Phys. Chem.1995, 99, 16646. doi: 10.1021/j100045a026
25. [25]
  (25) Yuan, J.;Wu, Q.; Zhang, P.; Yao, J.; He, T.; Cao, Y. Environ. Sci. Technol. 2012, 46, 2330. doi: 10.1021/es203333k
  (25) Yuan, J.;Wu, Q.; Zhang, P.; Yao, J.; He, T.; Cao, Y. Environ. Sci. Technol. 2012, 46, 2330. doi: 10.1021/es203333k

扫一扫看文章

计量

PDF下载量: 688
文章访问数: 1223
HTML全文浏览量: 45

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性

English

Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

不同浓度Sn4+离子掺杂TiO2的结构、性质和光催化活性

English

Structure, Characterization and Photocatalytic Properties of TiO2 Doped with Different Content of Sn4+ Ions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性

Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs